JPS585933B2 - Stabilized halogen-containing resin composition - Google Patents

Description

[Detailed description of the invention] The present invention relates to a stabilized halogen-containing resin composition.

More specifically, in the halogen-containing resin, In, Na, K, M
stabilized by adding a metal hydroxide or oxide or a basic inorganic acid salt and a metal complex salt of a β-diketone compound selected from g, Ca, Sr, Ba, Zn, Al, Zr, Sn The present invention relates to a halogen-containing resin composition.

Generally, halogenated resins have poor stability against heat and light, and tend to undergo thermal decomposition mainly due to dehydrohalogenation during thermoforming.

This causes a decline in the mechanical properties and color tone of processed products, resulting in significant disadvantages.

Therefore, in order to avoid such drawbacks, it has been necessary to add one or more kinds of thermal stabilizers to the resin to suppress thermal deterioration during processing steps.

Many metal soaps have been used for this purpose, with generally satisfactory results in terms of thermal stability.

However, among these metal soaps, cadmium soap, lead soap, etc. are highly toxic, and their use is currently largely restricted.

Therefore, it is necessarily necessary to use metal soaps or non-metallic stabilizers other than cadmium or lead soaps to obtain satisfactory thermal stability.

To this end, methods have been considered in which two or more types of non-toxic metal soaps or a combination of them and a non-metal stabilizer are used to achieve a synergistic effect.

However, although a certain degree of thermal stability can be obtained using such a method, the thermal stabilizing effect is considerably inferior to that when using cadmium or lead soap, and additional drawbacks arise, and the above-mentioned disadvantages arise. The method is insufficient to satisfy the technical problem as a stabilizer.

For example, the combination of a metal soap such as calcium, zinc, magnesium or barium with a polyhydric alcohol, diphenylthiourea or trisnonylphenyl phosphite has an insufficient stabilizing effect and is not suitable for practical use.

Further, although the combination with the above-mentioned metal soap brings about a certain degree of heat stabilizing effect, it has the disadvantage of lowering the softening point of the resin when it is hard compounded.

Furthermore, aminocrotonic acid ester has very poor compatibility with halogen-containing resins, and its effect is particularly insufficient for vinyl chloride resins obtained by suspension polymerization.

Furthermore, although dehydroacetic acid improves the initial coloration, it does not have a long-term stabilizing effect.

Moreover, it cannot be said that it is practically sufficient during molding.

For example, in the calender roll method, a plate-out phenomenon occurs on the roll surface, which impairs the surface shape of the molded product and significantly reduces processing efficiency.

This phenomenon of plate-out is observed in almost the same way in processing steps other than the calendar roll method, and is a drawback when stabilizing halogen-containing resins using metal soaps.

In order to solve these drawbacks associated with conventional stabilizers by using metal soaps other than cadmium and lead, the present inventors have conducted many years of research and found that they have excellent stability against deterioration due to light and heat. We have succeeded in developing a halogen-containing resin composition having the following properties.

That is, the present invention provides a halogen-containing resin containing Li, Na, K,
At least one metal hydroxide or oxide or basic inorganic acid salt selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Al, Zr and Sn and the following general formula [I
] The metal of the β-diketone compound (however, the metal is
The present invention relates to a stabilized halogen-containing resin composition characterized by adding a complex salt (selected from the group consisting of In, Na, K, Zn, Ba, and Ca).

(In the above formula, R1 represents a hydrogen atom, alkyl, aryl, alkylaryl, arylalkyl, or cycloalkyl group, R2 represents a hydrogen atom, alkyl, aryl, alkylaryl, arylalkyl group, or -C-R4, and R3 represents a hydrogen atom, an alkyl group, a halogen atom, or an alkoxy group.

R4 represents an alkyl or aryl group.

) The composition of the present invention having the above characteristics will be disclosed in detail and specifically below.

The first component of the composition of the present invention is Ii, Na, K, Mg, Ca
, Sr, Ba, Zn, Al, Zr and Sn, or a basic inorganic acid salt.

The above-mentioned hydroxides include compounds in which the above-mentioned metals are bonded only to hydroxyl groups, such as Mg(OH)2, Ca(OH)2,
Examples of the oxide include compounds of the above metals and oxygen, such as MgO
, CaO, BaO, Al2O3, SnO2, etc.

Moreover, these hydroxides or oxides may have crystal water.

Further, the basic inorganic acid salt is made of phosphoric acid, phosphorous acid, silicic acid, nitric acid, nitrous acid, sulfuric acid, sulfite, or boric acid, and the above metal or an oxide, hydroxide, or ammonium salt of the metal. For example, they can be synthesized in a conventional manner by reactions such as coprecipitation or melting, and they may be in the form of double salts, and may be anhydrous or contain water of crystallization.

Furthermore, any mixture of the above inorganic acid normal salt and a hydroxide or oxide may be used.

Preferred examples of this basic inorganic acid salt include the following compounds.

That is, 3CaO・Na3PO4, 5CaO・NaHPO
4,MgO・Mg3(PO4)2,3CaO・Ca3(
PO4)2, Ca(OH)2・Ca3(PO4)2,B
a(OH)2・Ca3(PO4)2・3H2O, Sr(
OH)2・Sr3(PO4)2, BaO・Ba3(PO
4) 2,3Ba(OH)2・Ba3(PO4)2,Zn
O・Zn3(PO4)2,2ZnO・Ba3(PO4)
2, Al2O3・AlPO4,3SnO・Sn3(PO
4) 2,Ba(OH)2・NaHPHO3,5CaO・
NaHPHO3,3Ba(OH)2・K2PHO3,M
gO・MgPHO3,5Mg(OH)2・MgPHO3
, CaO・CaPHO3,3Ca(OH)2CaPHO
3, Ba(OH)2・CaPHO3,5CaO・CaP
HO3,BaO・BaPHO3,2Ba(OH)2・B
aPHO3,3Ba(OH)2BaPHO・3H2O,
ZnO・ZnPHO3, ZnO・3CaPHO3, A1
2O3・Al2(PH03)3,3ZrO・ZrPHO
3, SnO・SnPHO3, 3SnO・SnPHO3,
Ng(OH)2Mg2SiO4,3MgO・MgSiO
3, MgO・K2Si03CaO・Ca2Si04,3
CaO-Li2Si03,3CaO・CaSi2O5,
2Ca(OH)2・Ca2Si3O8, SrO・SrS
iO3,5BaO・Ba2SiO4, Ba(OH)2,
Ba2SiO4・6H2O, Ba(OH)2・BaSi
O3,3Ba(OH)・BaSi2O5,3BaO・B
a2SiO4, Ba(OH)2・CaSiO3, 2Zn
O・ZnSiO3, ZnO・3CaSiO3, CaO・
Sn2SiO4, Mg(OH)・Mg(NO3)2,3
CaO・Ca(NO3)2,2Ca(OH)2Ca(N
O2)2・5H2O,3BaO・Ba(NO3)2,B
a(OH)2・Na2SO4, ZnO・K2SO4,3
CaO・K2SO3, Mg(OH)2MgSO4,5M
gO・MgSO3, 2MgO・MgSO3, MgO・C
aSO3,5CaO・CaSO4,Ca(OH)2・C
aSO4,3CaO・CaSO3, SrO・SrSO3
,3BaO・BaSO4,3BaO・CaSO3,Ba
(OH)2・BaSO4, Al2O3・Al2(SO4
)3, Al(OH)3・MgSO4, MgO・Mg3(
BO3)2, CaO・Ca3(BO3)2,5Ca(O
H)2・Ca3(BO3)2,3CaO・Ca(BO2
)2,3Ba(OH)2・Ba3(BO3)23BaO
・BaB4O7,5Ba(OH)2・Ba(BO2)2
.

The second component of the composition of the present invention is β represented by the general formula [I].
- A metal complex salt of a diketone compound (1,3-diketone compound).

Specifically, the alkyl group in general formula [I] includes methyl, ethyl, propyl, isopropyl, butyl,
Preferred examples include those having 1 to 18 carbon atoms, such as isobutyl, t-butyl, amyl, isoamyl, hexyl, heptyl, octyl, inoctyl, nonyl, decyl, isodecyl, undecyl, tridecyl, pentadecyl, and heptadecyl groups. The aryl group is preferably a phenyl group, the alkylaryl group is preferably an alkylphenyl group having an alkyl group having 1 to 12 carbon atoms, and the arylalkyl group is preferably an alkyl group having 1 to 12 carbon atoms.
Phenylalkyl having 4 alkyl groups is preferred.

Preferable examples of the cycloalkyl group include those having 6 to 8 carbon atoms, such as cyclohexyl and cyclooctyl groups.

Further, these groups may be substituted with an inert group such as an alkoxy group or a halogen atom.

Representative β-diketone compounds represented by the general formula [1] include penzoylacetylmethane, tribenzoylmethane, diacetylbenzoylmethane, and stearoyl.
Benzoylmethane, palmitoyl benzoylmethane,
lauroyl benzoylmethane, dibenzoylmethane,
4-methoxybenzoyl benzoylmethane, bis(4
-methoxybenzoyl)methane, bis(4-chlorobenzoyl)methane, bis(3,4-methylenedioxybenzoyl)methane, benzoyl acetyl octylmethane, benzoyl acetyl phenylmethane, stearoyl 4-methoxybenzoylmethane, bis (4-t-
butylbenzoyl)methane, benzoyl acetyl ethylmethane, benzoyl trifluoroacetylmethane, benzoyl formylmethane, benzoyl phenylacetylmethane, etc., and metal complex salts of these compounds (the metals are as described above) are used in the present invention. This is a representative example of the second component of the composition.

The amount of each component added in the present invention is 100% of the halogen-containing resin.
The amount of metal hydroxide or oxide or basic inorganic acid salt is 0.01 to 20 parts by weight, and β-
The amount of the metal salt of the diketone compound is preferably 0.001 to 1.0 parts by weight.

It goes without saying that metal organic acid salts (ordinary metal soaps) may also be used in combination with the composition of the present invention.

Examples of metal components in this case are Li, Na, K, Mg
, Ca, Ba, Zn, Sn, etc., and organic acid residues include the following carboxylic acid and phenol residues.

Examples of carboxylic acids include acetic acid, propionic acid, butyric acid,
Valeric acid, caproic acid, enanthic acid, caprylic acid, neoacid, 2-ethylhexylic acid, pelargonic acid, capric acid,
undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid,
1,2-hydroxystearic acid, behenic acid, monic acid, benzoic acid, monochlorobenzoic acid, P-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-
di-tert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cumic acid,
n-propylbenzoic acid, aminobenzoic acid, N,N-dimethylbenzoic acid, acetoxybenzoic acid, salicylic acid, P-
Monocarboxylic acids such as tert-octylsalicylic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, thioglycolic acid, mercaptopropionic acid, octylmercaptopropionic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, Adipic acid, pimelic acid, suric acid, azelaic acid, sebacic acid, fucuric acid, isofucric acid, terephthalic acid, oxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, aconitic acid , thiodipropionic acid, monoesters or monoamide compounds of divalent carboxylic acids such as hemimellitic acid, trimellitic acid,
Examples include di- or triester compounds of trivalent or tetravalent carboxylic acids such as merophanic acid, biromellitic acid, and mellitic acid.

Examples of phenols include tert-butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol, ethylphenol, isopropylphenol, inoctylphenol, -ethylhexylphenol, tert
Examples include -nonylphenol, decylphenol, tert-octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamylphenol, methylisohexylphenol, and methyl-t-octylphenol.

Of course, other additives may be added to the composition of the present invention to further improve its performance. Examples of these other additives include antioxidants, light stabilizers, crosslinking agent, filler, epoxy stabilizer, organic chelator,
Pigments, antistatic agents, antifogging agents, plate-out prevention agents, surface treatment agents, lubricants, flame retardants, fluorescent agents, antifungal agents, bactericidal agents, photodegrading agents, nonmetallic stabilizers, processing aids, mold release agents Agents and the like can be included.

As these other additives, conventionally well-known compounds can be used. For example, as antioxidants, phenol-based, amine-based, phosphite-based, and sulfur-based antioxidants are used. The one disclosed in Japanese Patent No. 49-78692 is used.

As the light stabilizer, penzophenone-based, penzotriazole-based, salicylate-based, substituted acrylonitrile-based, various metal salts or metal chelates, triazine-based, and piperidine-based light stabilizers can be used.
The material disclosed in Japanese Patent No. 9-78692 can be used.

Examples of the halogen-containing polymer used in the present invention include the following.

For example, polychlorinated polyvinylidene fluoride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, brominated polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer , vinyl styrene chloride copolymer, vinyl styrene chloride-butylene chloride copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl styrene chloride-maleic anhydride terpolymer, vinyl styrene chloride-acrylonitrile copolymer, chloride Vinyl butadiene copolymer, vinyl chloride-isobrene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-malein chloride Halogen-containing synthetic resins such as acid ester copolymers, vinyl chloride-methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymers, and internally plasticized polyvinyl chloride, or these resins and polyethylene, polypropylene, polybutene, polyester - Polyolefins such as α-olefin polymers such as 3-methylbutene, ethylene-vinyl acetate copolymers, ethylene-propylene copolymers, and copolymers thereof, polystyrene,
Polyvinyl acetate, acrylic resin, copolymers of styrene and other monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymers, acrylic ester-butadiene-styrene copolymers , a blend product with a methacrylic acid ester-butadiene-styrene copolymer, a block copolymer, or a graft copolymer.

The composition of the present invention is useful as a rigid PVC composition that cannot be used for lead-based stability, even among applications as a general halogen-containing resin composition.

Next, a concrete explanation will be given using examples.

However, the invention is not limited to the following examples.

In addition, initial colorability and thermal colorability in Examples were compared by determining yellowness using a Hunter colorimeter according to the formula below.

The degree of yellowness was as shown below when observed with the naked eye.

~6......Colorless and transparent 7-12...Colorless to slightly yellow 13-18.
......Slight yellow 19-24...Yellow 25-30...Yellow to orange 31-40
・・・・・・・・・Orange to yellowish brown 41～60・・・・・・
...brown to dark brown Example 1 The excellent stabilizing effect of the composition according to the present invention was investigated by the following method.

The formulation shown below was calendered to a thickness of 1 mm.
A 20 x 15 mm test piece was cut from this sheet and placed in a gear oven heated to 190°C to examine initial coloring, thermal coloring after 30 minutes, and thermal stability.

The results are shown in Table 1 below.

[Composition]

Polyvinyl chloride resin (Geon103EP) 100 weight Ba-stearate 0.3Ca-stearate 0.55Ca(OH)2・CaS
O4.1/2H2O2.0 stabilizing aid (Table 1) 0.1 Example 2 A test was conducted in the same manner as in Example 1 with the following formulation.

The results obtained are shown in Table 2 below.

[Formulation] Parts by weight Polyvinyl chloride resin (Geon103EP) 100 parts by weight TiO2 1.0 Low molecular weight polyethylene 0.5 Dibutyltin β-mercaptopropionate 0.1 Ca-stearate 1,0 Mg-stearate 0.5 parts by weight Dibenzoylmethane/Zn 0.3 parts by weight Indefinite salt compound (Table 2) 1.0 Example 3 A specimen was prepared using the following formulation, and the yellowing and blackening times at 190°C were measured. Obtained the results in the table.

Further, the volume resistivity (VR) was measured.

[Formulation] Parts by weight Polyvinyl chloride resin 100 Dioctyl phthalate (DOP) 50 parts by weight Calcium carbonate (SB) 20 Southern Clay #33 10Ba-stearate 0.5Zn-stearate
0.3Ca3(PO4)2
0.5Ca(OH)2
2.5 Stabilizing aids (Table 3)
0.1 Example 4 A sheet was made by hot pressing at 160°C using the following formulation.

Using this sheet, the yellowness in a 190°C gas oven and the volume resistivity (VR) at 30°C were measured.

Further, the yellowness of the sheet was also measured after press time of 10 minutes and 30 minutes at a press temperature of 170°C.

The results are shown in Table 4.

Part by weight Polyvinyl chloride resin (Geonl03EP) 100 Dioctyl phthalate 4050% Chlorinated paraffin 15 Calcium carbonate (SB) 20 Southern clay #33
10Ba-stearate
0.3Zn-stearate
0.2 dibenzoylmethane/Ca
0.1 Inorganic salt compounds (Table 4)
3.0 Example 5 The stabilizing effect in a polymer blend of polyvinyl chloride resin and ABS resin was evaluated in Example 1 using the following formulation.
was investigated using a similar test.

The results are shown in Table 5.

[Composition] Weight part: Polyvinyl chloride resin 80ABS resin
20 parts by weight

Claims (1)

[Claims] 1. The halogen-containing resin contains Li, Na, K, Mg, Ca,
At least one metal hydroxide or oxide or basic inorganic acid salt selected from the group consisting of Sr, Ba, Zn, Al, Zr and Sn, and β- represented by the following general formula [I] The metal of the diketone compound (however, the metal is Li, Na,
1. A stabilized halogen-containing resin composition characterized by adding a complex salt (selected from the group consisting of K, Zn, Ba and Ca). (In the above formula, R1 represents a hydrogen atom, alkyl, aryl, alkylaryl, arylalkyl, or cycloalkyl group, R2 represents a hydrogen atom, alkyl, aryl, alkylaryl, and aryl R4 represents an alkyl or aryl group. )